Method of metallizing azoic dyeings



United States Patent METHOD OF METALLIZING AZOIC DYEINGS.

Clemens Streck, Loudonville, N.Y., assignor to General Aniline & FilmCorporation, New York, N.Y., a corporation 'of'Delaware No Drawing.Application December 28, 1956 Serial No. 631,062

17 Claims. (Cl. 8-42) Thisinvention relates to an improved process ofmetallizing .azoic' dyeings and particularly to an improvedprocesswhereby said dyeings are obtained without the precipitation offree metal on the fibre and dyeing apparatus.

Itv is known that fibres may be impregnated with a coupling componentand passed into a solution which contains an active diazo, either in theform of a freshly prepared diazo or as a fast-color salt solution underconditions suitable for coupling. Fast color salts are diazo compoundswhich, except for a fewdiazos which are sufficiently stable per se, arediazo compounds which are stabilized by salt formation such as withcertain metallic salts, e.g. MgCl ZnCl SnCI etc., ar-yl-sulfonic acidssuch as naphthalened,S-disulfonic acid and naphthalene-1,3,6-trisulfonicacid, and alsoborofluoric acid.

One of theoutstanding advantages ofrazoic dyeings is their fastness incontrast to that of the. usual azo dyes. Thefastness of azoic dyeingshas recently. been improved by metallizing, i.e.- by treatingthe-previously dyed fibres with various metallizing agents-such as Cu,Co, Cr, Ni andthelike. In the art as nowpracticed, it isnecessary to dyethe fibrous material with an 'azoicdye devoid of solubilizing groupsfollowed'by anafter treatment'with a metallizing agent. The metallizingstep represents an extra step and also requires at least 20' minutes. Toovercome this, satisfactory metallization of azoic dyeings is achievedby incorporating the metallizingagent in the soaping bath as taught inmy. United States patent application (Serial No. 316,305), now UnitedStatesv States Patent 2,768,053.

-' In my United Statespatentapplicatibn Serial No. 601",- 658; filed onAugust 2, 1956, for Method of Metallizing Azoic Dyeings, I disclose andclaim a novel process whereby the azoic color formation is carried outin the presence of the metallizingagent. By this process fibrousmaterial dyed with an azoic dye, free from solubilizing groups: and'capable of conversion into a complex metal compound, is endowed withimproved light-, Washand chlorine-fastness properties and of improvedshade. In this process the: metallizing agent may be dissolved in anaphtholating bath, the fibrous. material impregnated with this bath,usually followed bydrying, and the impregnated fibre padded or printedwith an active diazo which includes a freshly prepared diazo or a diazostabilized as a fast color salt, and then metallizing; with hot wateror. preferably with steam. The temperature and moisture conditions ofthe hot Water or steam-are sufficiently drastic to yield completemetallization together with color development, even when exposed tosteamfor less than 1 minute. The important advantage of this improvedmethod is thata satisfactory metallized product isobtained without anyadditional operations other than the usual dyeing steps. By thisprocedure, economical dyeings are obtained as. contrasted with thepresent method of after metallizing which requires additional steps,over and above the dyeing steps, i.e'., treatment'with the metallizingagent andheating.

Despite the fact that economical dyeings having desirable'characteristics are obtained, the process neverthel'ess lacks one factorwhich is highly desirable in the dye trade. In conducting numerousexperiments with the process described in the aforesaid application,i.e., Serial No. 601,658, I found that under certain conditions, freecopper is precipitated. The precipitation may be on the fibre, causingsplotchy dyeings, or. in the dyeing apparatus, such as glass, steel,wood, stainless steel, etc. resulting in a metal plating problem. Theprecipitation is believed to be due tothe presence of certainimpuritiesor by-products which are'readily oxidizable and inoxidation' cause areduction of the. loosely coordinated copper salt to free copper.Cleaning oif deposited copper from equipment is diflicult in addition tothe poor, uneven dyeings resulting; therefrom.

I have found that precipitation can be very readily remedied by theaddition of an inorganic or organic oxidizing agent to the metallizingsolution. The metallizing solution and other details with regard to thediazo and coupling components employed in azoic dyeings are fullydescribed in my aforementioned patent application (Serial No. 601,658),.the disclosure of whichfis incorporated herein by reference thereto.The inorganic and organic oxidizing agentswhich I have foundparticularly useful include allof those'which are soluble in alkalineaqueous solutions, and are. sufficiently stable to withstand thetemperature. of padding which ranges from room temperature to 212 F.,and will not destroy the diazo com ponents. As illustrative examples ofsuch oxidizing agents, the following may be mentioned:

m-Nitrobenzenesulfonic acid p-Nitrobenzenesulfonic acid Sodium chromatePotassium chromate, Sodium perborate Potassium'perborate Sodium peroxidePotassium peroxide Hydrogen peroxide The foregoing oxidizing agents maybe present in the amount of about 10-100% based on the weight of themetallizing agent. As stated in myaforementioned patent application, themetallizing agents or compound employed in the metallizing of azoicdyeings are salts and hydroxides of copper (cupric). They are employedin the form of chlorides, sulphates, acetates, formates, nitrates, andthe like. Those compounds are preferred which are relatively Watersoluble or dispersible. The amount of copper salt or copper hydroxide,to be employed will usually depend on the degree of metallizing desired.Molar ratios are necessary for complete metallization' but the amountmay range from about a fraction of an equivalent to an excess of oneequivalent of metal perequivalent of dye. The preferred amount is about0.5 mol metal salt per mol of. dye.

The oxidizing agent maybe addedtothe metallizing solution together witha chelating agent and this solution employeddirectly to treat the fibrealone or in combination With'Naphthol AScompounds which are arylides of2 hydroxy 3-naphthoic acid and related p-hydroXy carboxylic, acidderivatives, acetoacetarylides and related ,3- oxocarboxylic acidarylides and pyrazolones. However, other compounds may be employed.which have active methylene or enolizable ketone groups and are freefrom Inst ad. of employing. a combination of the oxidizing agent,metallizing agent and chelating agent in the treatment, the chelatedmetallizing agent or oxidizing agent can becombined with a naphtholatingsolution or Rapidogen solution in the products per se or prior to dyeingand printing. A chelated metallizing agent in dry form and a suitableoxidizing agent can be incorporated in a dry naphthol or Rapidogenpowder. Further, the uncoordinated metal salt can be incorporated in adry naphthol or Rapidogen powder together with suitable oxidizing agent;however such mixture must be pasted with the proper chelating agentprior to use. While the above describes the addition of oxidizing agentto the naphthol or Rapidogen per se, it may be added at any time priorto use. The proportions of chelating agent, metallizing compound,Naphthol AS compound or Rapidogen powder are given in my pending patentapplication Serial No. 601,658. i

In order to practice one embodiment of the present invention, ametallizing solution is first prepared in accordance with the followingrecipe.

1 to 200 parts of metallizing compound 5 to 800 parts of water 1 to 30parts of chelating agent .5 to 80 parts of caustic soda (dry) Afterformation of the metallizing solution, 100% of an oxidizing agent isadded to the solution based on the weight of the metallizing compound.

The following examples will illustrate the preferred embodiments of thepresent invention. It is to be clearly understood that these examplesare illustrative and are not to be considered as limitative.

Example I A metallizing solution containing an oxidizing agent wasprepared as follows:

Copper solution 147 grams of copper sulfate 643 grams of water 110 gramsof tn'ethanolamine 60 grams of caustic soda (dry) After formation of ablue solution, 40 grams of sodium chromate anhydrous was added.

A padding solution was prepared by mixing the following components:

3 grams of Naphthol AS (3-hydroxy-2-naphthanilide) 6 cc. of ethylalcohol 1.5 cc. of caustic soda 34 B.

The padding solution Was poured into 10 cc. of the above copper solutiontogether with 2.5 cc. of caustic soda 34 B. and water to yield a totalvolume of 133 cc.

A 10 gram sample of muslin was padded with the above solution, dried andpadded with a solution consisting of:

7 grams of o-dianisidine, tetrazotized and stabilized with zincchloride,

.5 cc. of Diazopon AN (fatty alcohol-ethylene oxide condensation productused as a protective colloid) and 2 cc. of acetic acid 50% aqueoussolution. Suflicient water was added to give a total volume of 133 cc.

Example 11 Example I was repeated with the exception that the 'NaphtholAS in the padding solution was replaced by 2.

grams of phenyl methyl pyrazolone. A tan coloration was produced showingexcellent light-, washand chlorine-fastness without any perceivabletrace of copper precipitation on the fibre.

Example III Example I was repeated with the exception that the NaphtholAS was replaced by an equivalent amount ofZ-hydroxybenzeneazo-4-resorcinol and the o-dianisidine, tetrazotized andstabilized with zinc chloride, was replaced by an equivalent amount ofzinc chloride double salt of diazotized S-chloro-o-anisidine. A browndyeing was obtained which showed excellent light-, washandchlorine-fastness with no precipitation of metallic copper on the fibre.

Example IV Example I was again repeated with the exception that theNaphthol AS was replaced by an equivalent amount of3-hydroxy-2-naphthoic .acid o-toluidide and the o-dianisidine,tetrazotized and stabilized with zinc chloride, was replaced by anequivalent amount of zinc chloride double salt of the diazo fromS-n-butyl-sulfamyl-o-anisidine. A red dyeing was obtained which showedexcellent light-, washand chlorine-fastness with no evidence whatsoeverof copper precipitation on the fibre.

Example V A metallizing solution was prepared as follows:

Copper solutiongrams of tartaric acid 460 grams of water 100 grams ofcopper chloride 300 cc. of caustic soda 34 136.

After formation of a blue solution, 40 grams of sodium chromateanhydrous was added.

3 grams of B-hydroxy-Z-naphthanilide and 1 gram of his(acetoacet)-o-tolidide were dissolved in 100 cc. boiling watercontaining 4.5 cc. caustic soda 34 B. To this solution, cooled to about140 F., was added 10 cc. of the above copper solution.

A 10 gram sample of cotton was padded with the above solution and dried.It was then padded with a solution made by dissolving 8 /2 grams of zincchloride double salt of tetrazotized o-dianisidine, 0.5 cc. of a 40%solution of Diazopon AN solution, 13 cc. of 50% aqueous acetic acidsolution and water added to make up a total volume of 133 cc., followedby treatment with steam for 25 seconds. A deep jet black dyeing wasobtained of excellent wash-, lightand chlorine-fastness with no evidenceof deposition of metallic copper on the cotton fibre.

Example VI Example I was repeated with the exception that 10 cc. of thecopper solution described therein was replaced by an equivalent volumeof the following copper solution:

100 grams of glycine 400 grams of water 100 grams of copper chloride 300cc. of caustic soda 34 B. 100 grams of sodium perborate Example VIIExample I was repeated with the exception that 10 cc. of the coppersolution was replaced by an equivalent volume of the following coppersolution:

100 grams of glutamic acid 400 grams of water 100 grams of coppersulfate 300 grams of caustic soda 34 B6.

100 grams of m-nitrobenzenesulfonic acid Na salt Example VIII A solutionwas prepared from grams of a commercially available Rapidogen,consisting of 11 grams of o-dianisidine tetrazotized and stabilized withmethyl taurine; 11; igramslefi :lJrydroxy-Z-naplitlninilide; .10grams-of sodium hydroxide. (100%),80 cornbin'edwater and; solventsandSO-Tgrams of the'eo'pp'er solution prepared-aria Example 1. 11pm.- ofthe solution was thickened' with--v m ansct starch tr-agacanthandiaiiiusted l3- parts-ofwateri.

A gram samplcof cotton was'printed; with" the pasteysteainedfinacidasteamzin a normalimanri'e'r for 2 minutes," riiisedlandk-dfied'.The blue dyeing obtained showed excellentlightgiwash-r andchlorine-fastness with no evidence of metallic copper on the printedcotton 4 grams of a Rapidogen mix, con g oreanivalent amounts of cresidine diazotized and stabilized with sarcosine, '-liydroii3-fiitro 2liaphtliaiiilifle, '4 cc. of ethylene glycol mono ethylgethen i gtrcc.of water, 3 cc. of sodiurnhydroxide 34 Re and 5 cctpf copper solutioirof Example i'were combine arrdlO or. gumtia'g'acanthaddedt'oprintingtlrickrressi A 10 gram sample of cottoncloth was printed with the above paste and developed for 2 minutes inacidified steam. The bordeaux dyeing obtained showed excellent light-,washand chlorine-fastness with no evidence of metallic copper on theprinted cotton fibre.

Example X Example IX was repeated with the exception that 4 grams of theRapidogen mix was replaced by 4 grams of a Rapidogen mix consisting ofan equivalent amount of o-dianisidine tetrazotized and stabilized withmethyl taurine, and phenyl methyl pyrazolone and 10 cc. of coppersolution of Example I. A tan coloration was produced which showedexcellent light-, washand chlorine-fastness with no evidence of metalliccopper on the printed cotton fibre.

Example XI Example IX was again repeated with the exception that 4 gramsof the Rapidogen mix was replaced by 4 grams of a R-apidogen mixconsisting of an equivalent amount of4-benzoylamino-2-methoxy-5-rnethylaniline diazotized and stabilized withsarcosine, and 3-hydroxy- Z-naphthanilide. A violet shade somewhatredder than usual was produced having excellent light-, washandchlorine-fastness with no evidence of metallic copper on the printedcotton fibre.

I claim:

1. The process of producing metallized azoic prints and dyeings in situwhich comprises treating a cellulosic fibrous material selected from theclass consisting of cotton and regenerated cellulose with an azoiccoupling component devoid of solubilizing groups and a diazo componentderived from an amine base devoid of solubilizing groups to yield anazoic dye component capable of yielding an o,o'-dihydroxy azoconfiguration at elevated temperatures in the presence of a coordinatingagent selected from the class consisting of lower alkylolamines andaliphatic aminoand hydroxy-carboxylic acids, and a metallizing coppercompound consisting of soluble and dispersible salts and hydroxides ofcopper, and an oxidizing agent equivalent to 10l00% based on the weightof the metallizing agent, selected from the class consisting of alkaliperborates, alkali chromates, hydrogen peroxide, alkali peroxides andnitrobenzenesulfonic acids and their alkali salts.

2. The process according to claim 1 wherein the oxidizing agent issodium chromate.

3. The process according to claim 1 wherein the oxidizing agent issodium perborate.

4. The process according to claim 1 wherein the oxidizing agent ism-nitrobenzenesulfonic acid.

5. The process according to claim 1 wherein the oxidizing agent ispotassium chromate.

l 62 Theprocess of-producingmetallized azoic prints and} dyeings' insituwhichcomprises impregnating ;a cellulosiefibrous material selected fromthe class con sisting of cotton and regenerated cellulose with an azoiccoupling component devoid ofsolubilizing groups ata pH of, more than7followed by treatment with a diazonium compound derived from an aminebase devoid ofsolubilizing groups; and; which azoic component iscapable'of yielding.-an o,o dihydroxy azo dye configurationinj-the finaldye, followed by treatment at elevated temperatures in the presenceofacoordinating agent selected from the class consisting of loweralkylolamines an'd aliphatic aminoand hydroxy-carboxylic' acids, and a2metallizing coppercompound consisting ofsoluble and dispersible saltsand-hydroxides of copper, an'd'an oxidizing-"agent equivalent to 10-100%based on the Weight of the metallizing agent, selected from the classconsist- -ing=o alkali perborates, alkali chrom'ates, hydrogen peroxide,alkali peroxide s, and nitrobenzenesulfonic' acids and-theiralkalisalts: 72; The process of:producingmetallized azoic prints, insitu which comprises printing a cellulosic fibrous material selectedfrom the class consisting of cotton and regenerated cellulose with analkaline paste consisting of an azoic coupling component devoid ofsolubilizing groups and a diazoamino compound derived from an amine basedevoid of solubilizing groups, which has been diazotized and stabilizedwith a primary and secondary amine which contains at least onesolubilizing group, and which azoic dye component is capable of yieldingan o,o'-dihydroxy azo dye configuration in the final dye, followed bytreatment with acidified steam in the presence of a coordinating agentselected from the class consisting of lower alkylolamines and aliphaticaminoand hydroxy-carboxylic acids, and a metallizing copper compoundconsisting of soluble and dispersible salts and hydroxides of copper,and an oxidizing agent equivalent to 10-100% based on the weight of themetal- -lizing agent, selected from the class consisting of alkaliperborates, alkali chromates, hydrogen peroxide alkali peroxides andnitrobenzenesulfonic acids and their alkali salts.

8. A composition of matter for use in azoic dye manufacture whichcomprises an azoic coupling component devoid of solubilizing groups, acoordinating agent selected from the class consisting of loweralkylolamines and aliphatic aminoand hydroxy-carboxylic acids, ametallizing copper compound consisting of soluble and dispersible saltsand hydroxides of copper, and an oxidizing agent equivalent to Ill-%based on the weight of the metallizing agent, selected from the classconsisting of alkali perborates, alkali chromates, hydrogen peroxide,alkali peroxides and nitrobenzenesulfonic acids and their alkali saltsin an alkaline solution.

9. A composition of matter for use in azoic dye manufacture whichcomprises an azoic coupling component devoid of solubilizing groups,triethanolamine, copper sulfate and an oxidizing agent equivalent to10100% based on the weight of the metallizing agent, selected from theclass consisting of alkali perborates, alkali chromates, hydrogenperoxide, alkali peroxides and nitrobenzenesulfonic acids and theiralkali salts in an alkaline solution.

10. A composition according to claim 9 wherein the oxidizing agent issodium chromate.

11. A composition according to claim 9 wherein the oxidizing agent ispotassium chromate.

12. A composition according to claim 9 wherein the coupling component isNaphthol AS.

13. A composition of matter for use in azoic printing which comprises anazoic coupling component devoid of solubilizing groups, a diazoaminocompound derived from an amine base devoid of solubilizing groups whichhas been diazotized and stabilized with a primary and secondary aminecontaining at least one solubilizing group, which azoic dye componentsare capable'of yielding an o,o'-dihydroxy 'azo dye configuration in thefinal dye, a coordinating agent selected from the class consisting oflower alkylolamines and aliphatic aminoand hydroxy-carboxylic acids, anda metallizing copper compound consisting of soluble and dispersiblesalts and hydroxides of copper, and an oxidizing agent equivalent to10100% based on the weight of the metallizing agent, selected from theclass consisting of alkali perborates, alkali chromates, hydrogenperoxide, alkali peroxides and nitrobenzenesulfonic acids and theiralkali salts, in an alk-aline medium.

14. A composition of matter for use in azoic printing which comprises anazoic coupling component devoid of solubilizing groups, a diazoaminocompound derived from an amine base devoid of solubilizing groups whichhas been diazotized and stabilized with a primary and secondary aminecontaining at least one solubilizing group, which azoic dye componentsare capable of yielding an o,o'-dihydroxy azo dye configuration in thefinal 20 dye, triethanolamine, copper sulfate and an oxidizing agentequivalentto: 10-1009? based' on fth .weightiof the metallizing agent,selected from :the: class consisting of alkali perborates, alkalichromates, hydrogen peroxide, alkali peroxides and nitrobenzenesulfon'icacids; and their alkali sa1ts,'in an alkaline medium. i i z; 15. Thecomposition according to' claim .14 whei'ein the oxidizing agent issodium chromate. r

16. The composition according toclaim 14 wherein the diazois dianisidinetetrazotized and stabilized with methyl taurine, and the coupling.component isiNaphtholAS. I 1

17. The composition according to claim 14- wherein the diazo is4-benzoylamino 2-methoxy-5-methy1ani1ine diazotized and stabilizedwith.sarcosine, and, the coupling component is Naphthol v g 7 ReferencesClted in the tile o f thispatent I -FOREIGN. PATENTS 5 Great BritainMar. 7, 1939 Great Britain Jan. 6,1941

1. THE PROCESS OF PRODUCING METALLIZED AZOIC PRINTS AND DYEING IN SITU WHICH COMPRISES TREATING A CELLULOSIC FIBROUS MATERIAL SELECTED FROM THE CLASS CONSISTING OF COTTONN AND REGENERATED CELLULOSE WITH AN AZOIC COUPLING COMPONENT DEVOID OF SOLUBLIZING GROUPS AND A DIAZO COMPONENT DERIVED FROM AN AMINE BASE DEVOID OF SOLUBILIZING GROUPS TO YEILD AN AZOIC DYE COMPONENT CAPABLE OF YIELDING AN O,O''-DIHYDROXYAZO CONFIGURATION AT ELEVATED TEMPERATURES IN THE PRESENCE OF A COORDINATING AGENT SELECTED FROM THE CLASS CONSISTING OF LOWER ALKYLOLAMINES AND ALIPHATIC AMINO- AND HYDROXY-CARBOXYLIC ACIDS, AND A MELTALLIZING COPPER COMPOUND CONSISTING OF SOLUBLE AND DISPERSIBLE SALTS AND HYDROXIDES OF COPPER, AND AN OXIDIZING AGENT EQUIVALENT TO 10-1000% BASED FROM THE THE WEIGHT OF THE METALLIZING AGENT, SELECTED FROM THE CLASS CONSISTING OF ALKALI PERBORATES, ALKALI CHROMATES, HYDROGEN PERIOXIDE, ALKALI PEROXIDES AND NIRTOBENZENESULFONIC ACIDS AND THEIR ALKALI SALTS. 